CH3840E
Kinetics and Reactor Design
Assoc. Prof. Dr. Vu Dinh Tien
Dept. of Chemical Process Equiment –
School of Chemical Engineering
https://www.adelaide.edu.au/course-outlines/105526/1/sem-1/2022/
Topic 1
Introduction and Mole Balances
Fogler, Chapter 1
• Introduction
• Definitions
• General Mole Balance Equation: Batch, CSTR, PFR,
PBR
• Chemical Reaction Engineering Algorithm
Slide 5
How do we design a chemical reactor?
Type & size
Maximize the space-time yield of the desired product
(productivity kg/hr/m3)
Stoichiometry
Kinetics
Basic molar balances Reactor volume
Fluid dynamics
Use a lab-scale reactor to determine the kinetics!
Slide 7
Reactor Design
Reaction
Stoichiometry
Kinetics: elementary vs non-elementary
Single vs multiple reactions
Reactor
Isothermal vs non-isothermal
Ideal vs nonideal
Steady-state vs nonsteady-state
Slide 8
Chemical Reaction
• A detectable number of molecules have lost their
identity and assumed a new form by a change in the
kind or number of atoms in the compound and/or
by a change in the atoms’ configuration
o Decomposition CH3-CH3 H2 + H2C=CH2
o Combination N2 + O2 2NO
o Isomerization
• Rate of reaction
o How fast a number of moles of one chemical species are
being consumed to form another chemical species
Slide 11
Rate Law for rj
rA: the rate of formation of species A per unit volume [e.g., mol/m3•s]
-rA: the rate of a consumption of species A per unit volume
A B pr r A kCACB
1st order in A, 1st order in B, 2nd order overall
r A kCAn nth order in A
k1CA
rA Michaelis-Menton: common in enzymatic
1 k 2CA
reactions
rj depends on concentration and temperature:
Ea
RT
-rA Ae C Arrhenius dependence on temperature
A
A: pre-exponential factor EA : activation energy
R : ideal gas constant T:temperature
Slide 12
Basic Molar Balance (BMB)
Rate of Rate of Rate of
Rate of
flow of j flow of j + generation of j Rate of
- - decomposition =
into out of by chemical rxn accumulation
of j
system system
dN j
Fj0 Fj Gj
dt
mol mol mol d
mol
s s s dt
If the system is uniform throughout its entire volume, then:
G j rjV
Moles j Moles generated
generated per per unit time and Volume
unit time = volume (m3)
(mol/s) (mol/s•m3)
Slide 14
Batch Reactors Properties
• Reactants are placed in the reactor,
and the reaction is allowed to
proceed for some amount of time
• Closed system- no addition of
reactants or removal of products
during the reaction
• Unsteady-state conditions- the
composition changes with time
• Ideal batch reactor- vessel is
perfectly mixed
• Concentration and temperature are
spatially constant, but NOT constant
in TIME
Slide 18
Example 1: First Order reaction in a
Batch Reactor
• The gas phase reaction A→B+C will be carried out isothermally in
a 20 dm3 constant volume, well-mixed batch reactor.
• 20 moles of pure A is initially placed in the reactor.
• If the rate is –rA= kCA and k = 0.865 min-1, calculate the time needed
to reduce the number of moles of A in the reactor to 0.2 mol.
Ans: 5.32 min
Slide 21
Continuous Stirred Tank Reactor
(CSTR) Properties
• Continuously add reactants and
remove products (open system)
• Inlet stream instantaneously mixes
with bulk of reactor volume
• Ideal batch reactor- assume perfect
mixing occurs in vessel
• Temperature and concentration
are uniform throughout space
• Composition of the exit stream is
the same as that inside reactor
(CA,outlet = CA, tank)
• Steady-state conditions- the reaction
rate is the same at every point and
does not change with time
Link for CSTR
Slide 22
Examples of CSTRs
Laboratory-Scale Bioreactor
Pfaudler Inc.
Slide 23
Ideal SS CSTR Design Equation
Slide 25
Example 2: Second Order reaction in a
CSTR
• The reaction A→B is to be carried out isothermally in a continuous-
flow reactor.
• Calculate the CSTR volume to consume 99% of A (CA=0.01CA0)
when the entering molar flow rate is 5 mol A/h, the volumetric
flow rate is constant at 10 dm3/h and the rate is –rA= kCA2, where
k = 3 dm3/mol.h
Ans: 66000 dm3
Slide 26
Plug Flow Reactor (PFR) Properties
• Also called a tubular reactor
• Cylindrical pipe with openings
at both ends
• Steady movement of material
down length of reactor
• Reactants are consumed as they
flow down the length of the
reactor
• Operated at steady state:
o No radial variation in
temperature, concentration, or
reaction rate
o All fluid/gas elements have
the same residence time
Link for PFR
Slide 27
Industrial PFRs
Polyethylene reactor:
• 16 inch inner diameter
• Operates at 35,000 psi & 600 °F
•Has a vertical orientation when in use Courtesy
of Autoclave Engineers of Snap-tite, Inc.
Slide 28
Mole Balance – PFR
Slide 29
Example 3: First Order Reaction in PFR
• The first order reaction A B is carried out in a plug flow
reactor in which the volumetric flow rate, v, is constant.
Derive an equation relating the reactor volume to the entering
and exiting concentrations of A, the rate constant k, and the
volumetric flow rate, v.
• Determine the reactor volume necessary to reduce the exiting
concentration to 10% of the entering concentration when the
volumetric flow rate is 10 L/min and the rate constant, k, is
0.23 min-1.
Ans: 100 L
Slide 30
Example 4: Second Order reaction in a
PFR
•The reactionA→B is to be carried out isothermally in a
continuous-flow reactor.
•Calculate the PFRvolume to consume 99% of A (CA=0.01CA0)
when the entering molar flow rate is 5 mol A/h, the volumetric
flow rate is constant at 10 dm3/h and the rate is –rA= kCA2, where
k= 3 dm3/mol.h
Ans: 660 dm3
Slide 31
Mole Balance- Packed Bed Reactor
(PBR)
dFj Similar to PFR, but we want to express it in terms
r j
dV of catalyst weight instead of reactor volume
Units for the rate of a mol Units for the rate of mol
homogeneous rxn (rj) : s m 3 a catalytic rxn (rj’) : s kg catalyst
So rewriting the PFR design equation in terms of catalyst
weight instead of reactor volume:
dFj
rj ' where W is the weight of the catalyst
dW
Slide 33
Example 5: Derive equation for
Fluidised CSTR with catalyst particles
• Derive a reactor design equation for a fluidized CSTR
containing catalyst particles.
• The equation should be in terms of catalyst weight (W) and
the reaction rate for an equation that uses solid catalyst.
• Assume perfect mixing and steady-state operation of the
CSTR.
Slide 34
Reactor Mole Balances Summary
• The General Mole Balance applied to the four major reactor
types (and the general reaction A B )
Reactor Differential Algebraic Integral
NA
dN
dN A NA
Batch r AV t A
dt N rAV
A0
F FA t
CSTR V A0
rA
FA
dF
dFA
rA
V r A
FA
PFR dV
FA 0 A
FA
dF V
r
dFA FA
rA W A
PBR dW F A
A0
Slide 37
Selection of Reactors
Batch
• small scale
• production of expensive products (e.g. pharmacy)
• high labor costs per batch
• difficult for large-scale production
CSTR: most homogeneous liquid-phase flow reactors
• when intense agitation is required
• relatively easy to maintain good temperature control
• the conversion of reactant per volume of reactor is the smallest of the flow
reactors - very large reactors are necessary to obtain high conversions
PFR: most homogeneous gas-phase flow reactors
• relatively easy to maintain
• usually produces the highest conversion per reactor volume (weight of
catalyst if it is a packed-bed catalyze gas reaction) of any of the flow
reactors
• difficult to control temperature within the reactor
• hot spots can occur
Slide 38
Uses for Various Reactors
• Noncatalytic homogeneous gas Ethylene polymerization
reactor (high pressure)
• Homogeneous liquid reactor Mass polymerization of styrene
• Liquid-liquid reactor Saponification of fats
• Gas-liquid reactor Nitric acid production
• Non-catalytic gas-solid reactor Iron production
o Fixed bed Chlorination of metals
o Fluidized bed Ammonia synthesis
• Fixed bed catalytic reactor Catalytic cracking (petroleum)
• Fluid bed catalytic reactor Hydrodesulphurization of oils
• Gas-liquid-solid reactor
Slide 39
Topic 1: Summary
• From this workshop you should be able to:
1. Describe and define the rate of reaction;
2. Derive the general mole balance equation;
3. Apply the general mole balance equation to the four most common
types of industrial reactors (Batch, CSTR, PFR and PBR);
Slide 43
